CN106103546B - The manufacturing method of alkylene oxide polymer - Google Patents
The manufacturing method of alkylene oxide polymer Download PDFInfo
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- CN106103546B CN106103546B CN201580016137.9A CN201580016137A CN106103546B CN 106103546 B CN106103546 B CN 106103546B CN 201580016137 A CN201580016137 A CN 201580016137A CN 106103546 B CN106103546 B CN 106103546B
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- alkylene oxide
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- monohydric alcohol
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/08—Saturated oxiranes
- C08G65/10—Saturated oxiranes characterised by the catalysts used
- C08G65/12—Saturated oxiranes characterised by the catalysts used containing organo-metallic compounds or metal hydrides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/08—Saturated oxiranes
- C08G65/10—Saturated oxiranes characterised by the catalysts used
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/2645—Metals or compounds thereof, e.g. salts
- C08G65/266—Metallic elements not covered by group C08G65/2648 - C08G65/2645, or compounds thereof
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Abstract
The present invention provides a kind of manufacturing method for the alkylene oxide polymer that can industrially manufacture the high alkylene oxide polymer of the degree of polymerization with good reproducibility.A kind of manufacturing method of alkylene oxide polymer, it is the method for making alkylene oxide carry out polymerisation in unreactive hydrocarbons solvent in the presence of zinc catalyst and manufacturing alkylene oxide polymer, wherein, the zinc catalyst is obtained from making organic zinc compound and being reacted for the aliphatic polyol of 12 times of equivalents monohydric alcohol below and 0.2~1.1 times of equivalent relative to the organic zinc compound, and the amount of the monohydric alcohol in the polymerisation system carries out the polymerisation relative to the organic zinc compound for 0.01 times of equivalent condition below.
Description
Technical field
The present invention relates to the manufacturing methods of alkylene oxide polymer.More specifically, it is good to relate to industrially reproducibility
Ground manufactures the manufacturing method of the alkylene oxide polymer of the high alkylene oxide polymer of the degree of polymerization.
Background technology
Currently, the polymerization for alkylene oxide, especially ethylene oxide, propylene oxide etc., is carrying out many researchs.Example
Such as, it is known to product made of making organic zinc compound further be reacted with monohydric alcohol with product obtained from polyol reaction,
Or product obtained from making it be reacted with monohydric alcohol is further with product made of polyol reaction (for example, referring to patent text
It offers the 1,2) copolymerization relative to the alkylene oxide of the homopolymerization of alkylene oxide or two kinds or more and shows excellent catalyst activity, polymerize
Spend high polymer.
But in these methods, it is noted following problem：The degree of polymerization etc. of polymerization speed or obtained polymer
Reproducibility it is poor, and it is consolidated block etc. to be unable to get sufficient yield or polymerizate, industrially can not steadily be made
It makes.Moreover, being also not yet fully to meet in terms of the degree of polymerization.On the other hand, also attempt have the following method, with as point
It dissipates under the various minuteness particle metal oxides of auxiliary agent and the contact condition of nonionic surfactant, it is organic by using making
Zinc compound is used as catalyst with product (for example, referring to patent document 3) made of polyol reaction, is gathered with good reproducibility
Close object, but this method be noted catalyst modulation operations it is very troublesome.
As the above this method is solved the problems, such as, for example, motion has following methods in patent document 4：To making organic zinc
Product obtained from compound and aliphatic polyol and monohydric alcohol are reacted with specific equivalent proportion specific temperature range into
Row heat treatment, thus obtained substance is used as polymerization catalyst.
Existing technical literature
Patent document
Patent document 1：Japanese Patent Publication 45-7751 bulletins
Patent document 2：Japanese Patent Publication 53-27319 bulletins
Patent document 3：Japanese Unexamined Patent Application 62-232433 bulletins
Patent document 4：Japanese Unexamined Patent Publication 5-17566 bulletins
Invention content
Problems to be solved by the invention
But present inventor repeat inquire into as a result, it has been found that：Even such as that side disclosed in patent document 4
Method, the reproducibility for being also still polymerisation sometimes are deteriorated.
The present invention is the invention completed in view of this problem.That is, it is a primary object of the present invention to provide a kind of energy
The manufacturing method of enough alkylene oxide polymers for industrially manufacturing the high alkylene oxide polymer of the degree of polymerization with good reproducibility.
Solution for solving the problem
Present inventor has made intensive studies to solve that above-mentioned project.Itself the result shows that, even if by special
Method disclosed in sharp document 4 carries out the manufacture of catalyst under the same conditions, and can not similarly remove heat treatment causes
Unreacted monohydric alcohol in the case of, remaining monohydric alcohol makes catalyst activity change, sometimes the generations such as polymerization time
Deviation.Moreover, further repeat inquire into as a result, it has been found that, in the presence of zinc catalyst, make alkylene oxide in unreactive hydrocarbons solvent
Carry out in method of the polymerisation to manufacture alkylene oxide polymer, zinc catalyst be make organic zinc compound with it is organic relative to this
Obtained from zinc compound reacts for the aliphatic polyol of 12 times of equivalents monohydric alcohol below and 0.2~1.1 times of equivalent, and it is logical
The amount for the monohydric alcohol crossed in polymerisation system is that 0.01 times of equivalent is gathered under the conditions of below relative to organic zinc compound
Reaction is closed, can industrially manufacture the high alkylene oxide polymer of the degree of polymerization with good reproducibility.The present invention is by being based on these
Opinion further repeats to inquire into and the invention of completion.
That is, the present invention provides the invention of following disclosed modes.
A kind of 1. manufacturing methods of alkylene oxide polymer of item, are to make alkylene oxide in the presence of zinc catalyst in unreactive hydrocarbons
The method for carrying out polymerisation in solvent and manufacturing alkylene oxide polymer, wherein
The zinc catalyst is to make organic zinc compound and is that 12 times of equivalents are below relative to the organic zinc compound
Obtained from the reaction of the aliphatic polyol of monohydric alcohol and 0.2~1.1 times of equivalent,
The amount of monohydric alcohol in the polymerisation system is 0.01 times of equivalent or less relative to the organic zinc compound
Condition carry out the polymerisation.
A kind of 2. manufacturing methods of alkylene oxide polymer of item, are to make alkylene oxide in the presence of zinc catalyst in unreactive hydrocarbons
The method for carrying out polymerisation in solvent and manufacturing alkylene oxide polymer, has：
Make organic zinc compound with relative to the organic zinc compound be 12 times of equivalents monohydric alcohol below and 0.2~
The aliphatic polyol reaction of 1.1 times of equivalents, the process for preparing reaction solution；
By the reaction solution under normal pressure, 100 DEG C of temperature or less distill, prepare make the amount of the monohydric alcohol relative to
The organic zinc compound is the process of 0.01 times of equivalent zinc catalyst below；And
It is catalyzed for 0.01 times of equivalent zinc below relative to the organic zinc compound using the amount of the monohydric alcohol
The process that agent makes the alkylene oxide polymerization reaction.
The manufacturing method of alkylene oxide polymer of the item 3. according to item 1 or item 2, wherein
The organic zinc compound is dialkyl group zinc.
The manufacturing method of alkylene oxide polymer of the item 4. according to any one of 1~item of item 3, wherein
The monohydric alcohol is the aliphatic alcohol of carbon atom number 1~3.
The manufacturing method of alkylene oxide polymer of the item 5. according to any one of 1~item of item 4, wherein
The aliphatic polyol is that the aliphatic with 2 or more hydroxyls during carbon atom number is 2 or more and molecule is more
First alcohol.
A kind of manufacturing method of the catalyst of 6. polymerisation zinc for alkylene oxide of item, has：
Make organic zinc compound with relative to the organic zinc compound be 12 times of equivalents monohydric alcohol below and 0.2~
The reaction process of the aliphatic polyol reaction of 1.1 times of equivalents；And
By the reaction solution obtained by the reaction process under normal pressure, 100 DEG C of temperature or less distill, make described one
The amount of first alcohol is 0.01 times of equivalent process below relative to the organic zinc compound.
A kind of zinc catalyst of 7. polymerisations for alkylene oxide of item, wherein
Make organic zinc compound with relative to the organic zinc compound be 12 times of equivalents monohydric alcohol below and 0.2~
After the aliphatic polyol reaction of 1.1 times of equivalents, by obtained reaction solution under normal pressure, 100 DEG C of temperature or less distill, make
The amount of the monohydric alcohol is 0.01 times of equivalent or less relative to the organic zinc compound.
Invention effect
The manufacturing method of alkylene oxide polymer according to the present invention can manufacture the high alkylene oxide of the degree of polymerization with good reproducibility
Polymer.
Specific implementation mode
1. the manufacturing method of alkylene oxide polymer
The manufacturing method of the alkylene oxide polymer of the present invention is to make alkylene oxide in the presence of zinc catalyst, molten in unreactive hydrocarbons
The method for carrying out polymerisation in agent to manufacture alkylene oxide polymer, which is characterized in that zinc catalyst is to make organic zinc compound
It is reacted with the aliphatic polyol relative to organic zinc compound for 12 times of equivalents monohydric alcohol below and 0.2~1.1 times of equivalent
Obtained from, under the conditions of the amount of the monohydric alcohol in polymerisation system is below for 0.01 times of equivalent relative to organic zinc compound
Carry out polymerisation.Hereinafter, the manufacturing method for the alkylene oxide polymer that the present invention will be described in detail.
In the manufacturing method of the alkylene oxide polymer of the present invention, the alkylene oxide as raw material for polymerisation does not limit especially
System, such as ethylene oxide, propylene oxide, epoxy butane, 7-oxa-bicyclo[4.1.0, styrene oxide, epoxychloropropane can be enumerated etc..This
In a little alkylene oxides, it is preferable to use ethylene oxide, epoxy from the viewpoint of obtained alkylene oxide polymer is to the dissolubility height of water
Propane etc..These alkylene oxides can use individually, and can also combine two or more use.It should be noted that being used alone
The polymer of alkylene oxide is the homopolymer of the alkylene oxide, and it is these epoxies that alkylene oxide, which is combined the polymer that two or more is used,
The copolymer of alkane.The alkylene oxide polymer of manufacturing method manufacture through the invention can be block copolymer, can also be nothing
Advise copolymer.
It as the unreactive hydrocarbons solvent for polymerisation, is not particularly limited, but preferably enumerates：Pentane, n-hexane, positive heptan
The aliphatic hydrocarbon of alkane, hexamethylene etc.；Aromatic hydrocarbons such as benzene,toluene,xylene etc..In these solvents, from industrially being easy to start with
From the perspective of, more preferably use n-hexane, normal heptane etc..These solvents can use individually, can also combine 2 kinds with
Upper use.
As the usage amount of the unreactive hydrocarbons solvent in polymerisation, be not particularly limited, but from make polymerisation efficiently into
Capable viewpoint, inhibit the alkylene oxide polymer as product as block from the perspective of, can enumerate relative to alkylene oxide 100
Mass parts, preferably 200~10000 mass parts, more preferably 300~1000 mass parts, further preferably 400~600 matter
Measure part.
In the present invention, the zinc catalyst for polymerisation is to make organic zinc compound and relative to the organic zinc compound
Obtained from the reaction of the aliphatic polyol of 12 times of equivalents monohydric alcohol below and 0.2~1.1 times of equivalent.As be described hereinafter, this hair
In bright, after being prepared for such reaction solution, make the reaction solution under normal pressure and 100 DEG C of temperature or less distills unreacted unitary
Alcohol, it is 0.01 times of equivalent zinc catalyst below thus to obtain the amount of monohydric alcohol relative to organic zinc compound, can be used
In the polymerisation that the zinc catalyst carries out.At this point, the amount of the monohydric alcohol in polymerisation system is relative to organic zinc compound
Below 0.01 times of equivalent.It, can industrially with good reproducibility by carrying out polymerisation in such a situa-tion in the present invention
Manufacture the high alkylene oxide polymer of the degree of polymerization.
Organic zinc compound used in the preparation of zinc catalyst is general formula：ZnR2Compound represented.In general formula, as
R separately enumerates the alkyl of carbon atom number 1~6, the naphthenic base etc. of phenyl, carbon atom number 4~6.As organic zinc chemical combination
The concrete example of object can enumerate the dialkyl group zinc such as zinc methide, diethyl zinc, diη-propyl zinc, dibutyl zinc；Diphenyl zinc, two
Cyclobutyl zinc etc..Wherein, preferred dialkyl group zinc, particularly preferred diethyl zinc.
Monohydric alcohol used in the preparation of zinc catalyst is to have in molecule there are one hydroxyl and do not have reactive hydrogen in addition
Alcohol.As the concrete example of monohydric alcohol, such as can enumerate：The primary alconols such as methanol, ethyl alcohol, 1- propyl alcohol, n-butyl alcohol；2- propyl alcohol, 2- butanol
Equal secondary alcohol；Tertiary alcohols such as the tert-butyl alcohol etc..Wherein, due to needing unreacted monohydric alcohol being efficiently discharged in aftermentioned distillation
Outside system, the monohydric alcohol that it is advantageous to the boiling point under normal pressure be 100 DEG C or less and carbon atom number is 1~3, specifically, it is preferable that
Use the aliphatic alcohol of the carbon atom numbers 1~3 such as methanol, ethyl alcohol, 2- propyl alcohol.These monohydric alcohols can use individually, and also may be used
To combine two or more use.
In the preparation of zinc catalyst, for the upper limit value of the usage amount of monohydric alcohol, it is distilled off from by aftermentioned
Unreacted monohydric alcohol and the amount of unreacted monohydric alcohol relative to organic zinc compound be 0.01 times of equivalent condition below
Under carry out polymerisation with good reproducibility from the perspective of, need to be set as 12 times of equivalents or less relative to organic zinc compound.Make
For the upper limit value of the usage amount of monohydric alcohol, preferably 10 times of equivalents hereinafter, below more preferably 8 times of equivalents.As monohydric alcohol
The lower limiting value of usage amount can be enumerated from the viewpoint of the activity for the zinc catalyst for keeping obtaining relative to organic zinc compound,
More than preferably 1 times of equivalent, more than more preferably 2 times of equivalents, more than further preferably 3 times of equivalents.As making for monohydric alcohol
The preferred range of dosage can be enumerated relative to organic zinc compound, preferably 1~12 times of equivalent, and more preferably 2~10 times are worked as
Amount, further preferably 3~8 times of equivalents.
The aliphatic polyol used in the preparation of zinc catalyst be carbon atom number be 2 or more and molecule in have 2 with
On hydroxyl aliphatic polyol.As the concrete example of aliphatic polyol, can enumerate：Ethylene glycol, propylene glycol, 1,2- fourths two
Alcohol, 1,3 butylene glycol, 1,4- butanediols, 2,3- butanediols, 1,5- pentanediols, penta triols of 2,3,4-, 1,6-HD, glycerine,
Pentaerythrite etc..Wherein, from the viewpoint of the activity of obtained zinc catalyst, the preferably aliphatic polybasic of carbon atom number 4
Alcohol, specifically, it is preferable that using 1,3-BDO, 1,4-butanediol.
For the upper limit value of the usage amount of aliphatic polyol, alkylene oxide polymerization is manufactured from the zinc catalyst used
When object, from the perspective of the generation for preventing the block of alkylene oxide polymer, need relative to organic zinc compound be 0.2~
1.1 times of equivalents.The preferred range of usage amount as aliphatic polyol, it is 0.3 that can enumerate relative to organic zinc compound
~1.0 times of equivalents.
It is smooth from when organic zinc compound, monohydric alcohol and aliphatic polyol being made to react in the preparation of zinc catalyst
, it is preferable to use reaction dissolvent from the perspective of ground is reacted.It as reaction dissolvent, is not particularly limited, such as can enumerate just
The aliphatic hydrocarbons such as pentane, n-hexane, normal heptane, hexamethylene；Aromatic hydrocarbons such as benzene,toluene,xylene etc..It should be noted that
In above-mentioned polymerisation, from the viewpoint of efficiently manufacturing alkylene oxide polymer, it is used to prepare the solvent of zinc catalyst
It is preferable to use identical solvents with the unreactive hydrocarbons solvent of the polymerisation for alkylene oxide.
In the preparation of zinc catalyst, as the usage amount of solvent, the viewpoint of viewpoint and control reaction heat economically
It sets out, can enumerate relative to 100 mass parts of organic zinc compound, preferably 200~1500 mass parts, more preferably 300~
1200 mass parts, further preferably 400~1000 mass parts.
In addition, in the preparation of zinc catalyst, from when organic zinc compound, monohydric alcohol and aliphatic polyol being made to react,
From the perspective of keeping the obtained activity of zinc catalyst, preferably under the inactive gas environment such as nitrogen, argon gas and helium into
Row.
In the preparation of zinc catalyst, as the side for making organic zinc compound, monohydric alcohol and aliphatic polyol reaction
Method is not particularly limited, such as can enumerate：(a) it after adding solvent and organic zinc compound, is reacted with a part of monohydric alcohol,
Then, the method for making remaining monohydric alcohol and aliphatic polyol react；(b) after adding solvent and organic zinc compound, with
A part of aliphatic polyol reaction, the method for then reacting monohydric alcohol and remaining aliphatic polyol；(c) it adds molten
After agent and organic zinc compound, the method etc. that makes monohydric alcohol and aliphatic polyol simultaneous reactions.
It should be noted that in the method for above-mentioned (a), as the amount for making initial a part of monohydric alcohol react, can lift
Go out relative to organic zinc compound, more than preferably 0.2 times of equivalent, more than more preferably 0.4 times of equivalent.In addition, at above-mentioned (b)
Method in, as the amount for making initial a part of aliphatic polyol react, can enumerate relative to organic zinc compound, preferably
More than 0.1 times of equivalent, more than more preferably 0.2 times of equivalent.
As above-mentioned, in the manufacturing method of the present invention, under normal pressure by the reaction solution prepared by method as described above
And 100 DEG C of temperature or less distill, be removed until reaction solution in monohydric alcohol amount relative to organic zinc compound be 0.01
Until below times equivalent, it is the zinc catalysis below of 0.01 times of equivalent to obtain the amount of monohydric alcohol as a result, relative to organic zinc compound
Agent.In the present invention, by using such zinc catalyst, can the monohydric alcohol in polymerisation system amount relative to organic zinc
Compound is to carry out polymerisation under the conditions of 0.01 times of equivalent is below, can industrially manufacture degree of polymerization height with good reproducibility
Alkylene oxide polymer.
The upper limit of temperature when as distillation reaction liquid, for the quantity of the active site of the zinc catalyst kept, and
Its activity is kept, is preferably 100 DEG C or less under normal pressure.As the upper limit of the vapo(u)rizing temperature, 90 DEG C are more preferably enumerated.Another party
Face, from the activity reduction that zinc catalyst outside unreacted monohydric alcohol or the abundant discharge system of aliphatic polyol, will be prevented and partially
From the perspective of difference, as the lower limit of the vapo(u)rizing temperature, preferably 70 DEG C.As the range of vapo(u)rizing temperature, 70 DEG C are preferably enumerated
~90 DEG C.It should be noted that in the present invention, vapo(u)rizing temperature is the temperature for the heat medium for heating reaction vessel.
It as the number distilled, is not particularly limited, but is filled from by unreacted monohydric alcohol or aliphatic polyol
Divide outside discharge system, from the perspective of the activity reduction and the deviation that prevent zinc catalyst, can enumerate preferably 2 times or more, it is more excellent
It is selected as 3 times or more.It should be noted that when carrying out 2 times or more multiple distillations, the 2nd later each distillation of beginning it
Before, solvent of the preferably appropriate addition for polymerisation.It as the additive amount of the solvent, is not particularly limited, but from distillation
Purpose and economically from the perspective of, can enumerate relative to 100 mass parts of organic zinc compound, preferably 400~1000 mass
Part.
In turn, in the present invention, zinc catalyst can also further be carried out at heating after having carried out above-mentioned distillation
Reason.It can be enumerated preferably from the viewpoint of the activity for the zinc catalyst for keeping obtaining as the upper limit value of heat treatment temperature
200 DEG C hereinafter, more preferably 150 DEG C or less.In addition, the lower limiting value as heat treatment temperature, from by unreacted monohydric alcohol
Or outside the abundant discharge system of aliphatic polyol, from the perspective of inhibiting active attenuating, deviation of zinc catalyst etc., it can enumerate excellent
It is selected as 100 DEG C or more, more preferably 120 DEG C or more.As the range of heat treatment temperature, preferably 100~200 can be enumerated
DEG C, more preferably 120 DEG C~150 DEG C.It should be noted that in the present invention, heat treatment temperature is heating reaction vessel
The temperature of heat medium.
Time needed for heat treatment is different due to heating temperature, but reduced from the activity for the zinc catalyst for inhibiting to obtain,
From the perspective of active deviation etc., can usual 5~180 minutes, preferably 10~60 minutes range suitable for determine.
In the manufacturing method of the alkylene oxide polymer of the present invention, the amount of the monohydric alcohol in polymerisation system is relative to above-mentioned
Organic zinc compound, need for below 0.01 times of equivalent.That is, it needs to by the amount of the monohydric alcohol in above-mentioned zinc catalyst relative to
Above-mentioned organic zinc compound is that 0.01 times of equivalent compound below is used for polymerisation.Monohydric alcohol amount relative to organic zinc
In the case that compound is more than 0.01 times of equivalent, the activity of zinc catalyst generates deviation, as a result, the polymerization time production of alkylene oxide
Raw deviation, and the performance (especially viscosity) of obtained alkylene oxide generates deviation.It should be noted that the unitary in zinc catalyst
The amount of alcohol is the value obtained by aftermentioned assay method.
It, can also be by adjusting solvent if the zinc catalyst of above-mentioned preparation is used directly for the polymerisation of alkylene oxide
Amount and used suitable for adjustment concentration.It should be noted that the adjustment of concentration such as can by above-mentioned distillation in remove
Or solvent is added to carry out.
As make alkylene oxide in the presence of zinc catalyst, in unreactive hydrocarbons solvent polymerisation method, do not limit especially
It is fixed, for example, above-mentioned unreactive hydrocarbons solvent and zinc catalyst are added in polymerization container, alkylene oxide is further added,
The method that it is polymerize in inactive gas environment.In addition, in the polymerization, from the viewpoint for swimmingly carrying out polymerisation
It sets out, preferably stirs or vibrate on one side, carry out on one side.
It as the usage amount of the zinc catalyst in polymerisation, is not particularly limited, but from efficiently carrying out polymerisation
From the perspective of, it can enumerate on the basis of the zinc atom in the zinc catalyst relative to the molal quantity of alkylene oxide, preferably 0.01
~1 mole of %, the range of more preferably 0.02~0.8 mole %.
It, can be according to reaction conditions such as the type of alkylene oxide, concentration, the concentration of zinc catalyst as the temperature of polymerisation
It arbitrarily sets, but usually 5~100 DEG C, preferably 20~50 DEG C.In addition, as the pressure in polymerisation, without special
Limitation, such as 0.0MPa~1.0MPa, preferably 0.01MPa~0.5MPa can be enumerated.
As the terminal of polymerisation, such as 15 minutes unchanged moment works can be continued with the internal pressure in paradigmatic system
For the terminal of reaction.After polymerisation, by being dried, alkylene oxide polymer is obtained.In this way, obtained alkylene oxide
Polymer is typically non-consolidated block and to be thin shot-like particle can obtain viscosity with good reproducibility in aftermentioned assay method
For the alkylene oxide polymer of 300mPa.s or more.
In the present invention, using the zinc catalyst prepared as above, the amount of the monohydric alcohol in polymerisation system relative to
Organic zinc compound is to carry out polymerisation under the conditions of 0.01 times of equivalent is below, it is possible thereby to industrially make with good reproducibility
The high alkylene oxide polymer of the degree of polymerization is made, the details of mechanism are still not clear, but can for example consider as follows.I.e., it is generally recognized that
It is following mechanism：In the polymerization using the alkylene oxide of organic zinc compound, it is coordinated alkylene oxide on zinc and carries out open loop successively
Addition.Such as the present invention, since the amount of existing unreacted monohydric alcohol in the polymerization is considerably less, to zinc catalyst occur
Catalyst activity improve and stabilize, be as a result regarded to manufacture the high alkylene oxide polymer of the degree of polymerization with good reproducibility.
The alkylene oxide polymer manufactured in the manufacturing method of the present invention is to supply useful polymer for various purposes.For example,
Ethylene oxide polymer is throughout paper grade (stock) dispersant, agglutinant, water-solubility membrane, water-soluble subtle, printing and dyeing paste, plasticizer
Etc. various aspects can be used as useful water-soluble macromolecule.
2. zinc catalyst
In the present invention, the manufacture of alkylene oxide polymer can be carried out by above-mentioned zinc catalyst.The feature of the zinc catalyst
It is, makes organic zinc compound and be 12 times of equivalents monohydric alcohol below and 0.2~1.1 times relative to the organic zinc compound
After the aliphatic polyol reaction of equivalent, by obtained reaction solution under normal pressure, 100 DEG C of temperature or less distill, make unitary
The amount of alcohol is 0.01 times of equivalent or less relative to organic zinc compound.In addition, the zinc catalyst can pass through process system below
It makes.
Make organic zinc compound with relative to the organic zinc compound be 12 times of equivalents monohydric alcohol below and 0.2~1.1
The reaction process of the aliphatic polyol reaction of times equivalent
By the reaction solution obtained in reaction process under normal pressure, 100 DEG C of temperature or less distill, make the amount of monohydric alcohol
It is 0.01 times of equivalent process below relative to organic zinc compound
In the zinc catalyst of the present invention, for the alkylene oxide of polymerization, the organic zinc compound for manufacturing zinc catalyst, one
First alcohol, aliphatic polyol, reaction condition are for example above-mentioned.
By the way that the zinc catalyst of the present invention to be used for the polymerisation of alkylene oxide, can industrially manufacture with good reproducibility
The high alkylene oxide polymer of the degree of polymerization.
Embodiment
Simultaneously the present invention will be described in detail for following presentation Examples and Comparative Examples.But the present invention is not limited to embodiments.
[evaluation method]
The performance of the alkylene oxide polymer obtained in each Examples and Comparative Examples is measured by the following method, is evaluated.Table 1
And table 2 indicates result.
(1) measurement of viscosity
Into the beaker of 1L volumes be added ion exchange water 497.5g, with wide 80mm, long 25mm tablet in front end peripheral speed
To be stirred under conditions of 1.0m/s, while alkylene oxide polymer 2.5g is put into, continues stirring 3 hours, prepare aqueous solution.It will
Obtained aqueous solution impregnates 30 minutes or more in 25 DEG C of thermostat, and with Type B rotational viscometer, (Type B of TOKIMEC societies is viscous
Degree meter, rotor number 2, rotating speed 12rpm, 3 minutes, 25 DEG C) find out the viscosity of aqueous solution.
It should be noted that if viscosity is 300mPas or more, can determine whether as the high alkylene oxide polymerization of the degree of polymerization
Object.
(2) measurement of monohydric alcohol amount
For the measurement of monohydric alcohol amount, gas chromatography (GC-2014, society of Shimadzu Seisakusho Ltd. system, hereinafter referred to as are used
GC), in 200 DEG C of gasification temperature, use column Thermon1000 (length：3 meters), 100 DEG C of column temperature, 200 DEG C of detector temperature
Under the conditions of be measured, concentration is calculated according to peak area.Monohydric alcohol amount is calculated according to the calibration curve being generated in advance.
[embodiment 1-1]
(manufacture of zinc catalyst)
Prepare to have cooler, dropping funel, nitrogen ingress pipe, as blender with 4 blade diameter 53mm
The paddle of (45 degree of inclinations) blade, internal diameter 80mm, 500mL volume round-bottomed flask.
N-hexane 87.1g, diethyl zinc (Et is added in flask after nitrogen displacement2Zn) 9.90g, inside at 20 DEG C of temperature
It is stirred with front end peripheral speed 0.97m/ seconds (speed of agitator 350rpm), meanwhile, as the first stage, on one side with 0.2g/ minutes
Ethyl alcohol (EtOH) 11.03g (0.240 mole) is added dropwise to be reacted on one side.As second stage, by 1,4-butanediol (Isosorbide-5-Nitrae-
BDO) in the mixed liquor of 6.49g (0.072 mole) and ethyl alcohol 13.27g (0.288 mole) were added drop-wise to 0.2g/ minutes and are cooled to
In the reaction solution of 10 DEG C of temperature.After completion of dropwise addition, it will be warming up to 30 DEG C in flask and react 1 hour, then, be warming up to 50 DEG C of reactions 1
Hour.Later, with 80 DEG C of heating of oil bath temperature, the removing of unreacted component is carried out by distillation.It is let cool after distillation to room temperature, is added
Add n-hexane 52.4g and with oil bath temperature 80 DEG C heated, carry out the 2nd time distillation.1 operation is further carried out again, into
Total 3 distillations of row.After 3 distillations, moves in the pressure vessel replaced by fully nitrogen, cover tightly and with oil bath temperature
130 DEG C of heat treatment for carrying out 15 minutes.It after cooling, is diluted with n-hexane 264g, the zinc for obtaining the zinc containing 1.8 mass % is urged
Agent 297g.The n-hexane of the supernatant of the zinc catalyst is measured by GC, amount of alcohol is relative to organic zinc compound
0.0033 times of equivalent.
(manufacture of alkylene oxide polymer)
Prepare have dropping funel, nitrogen ingress pipe, the anchor type blade with blade diameter 47mm as blender
Paddle, internal diameter 94mm, 1L volume pressure-resistant reaction vessel.
N-hexane 340g is added in the pressure vessel after fully being replaced by nitrogen, makes zinc catalyst obtained above
(zinc converts 0.975g：0.0004 mole) it is evenly dispersed, ethylene oxide 81g (1.84 moles) is added and covers tightly, at 40 DEG C
It polymerize while stirring in thermostat.After polymerization, white product is taken out in filtering, is dried under reduced pressure, is gathered at 40 DEG C
Ethylene oxide 81.0g.
Polymerization time is 6 hours, and yield is 100 mass %.The aqueous solution of 0.5 mass % of obtained polyethylene oxide
Viscosity is 855mPa.s.
[embodiment 1-2]
It is manufactured in the same manner as embodiment 1-1, obtains the zinc catalyst 297g of the zinc containing 1.8 mass %.It is measured by GC
The n-hexane of the supernatant of the zinc catalyst, as a result amount of alcohol is 0.0038 times of equivalent relative to organic zinc compound.
In the same manner as embodiment 1-1, make (1.84 moles) polymerizations of ethylene oxide 81g using above-mentioned zinc catalyst, as a result
To polyethylene oxide 79.5g.
Polymerization time is 6 hours, and yield is 98 mass %.The aqueous solution of 0.5 mass % of obtained polyethylene oxide
Viscosity is 825mPa.s, and reproducibility is good.
[embodiment 1-3]
Zinc catalyst is manufactured in the same manner as embodiment 1-1, obtains the zinc catalyst 297g of the zinc containing 1.8 mass %.It is logical
The n-hexane that GC measures the supernatant of the zinc catalyst is crossed, amount of alcohol is 0.0047 times of equivalent relative to organic zinc compound.
In the same manner as embodiment 1-1, make (1.84 moles) polymerizations of ethylene oxide 81g using above-mentioned zinc catalyst, as a result
To polyethylene oxide 80.7g.
Polymerization time is 45 minutes 6 hours, and yield is 100 mass %.The water of 0.5 mass % of obtained polyethylene oxide
The viscosity of solution is 865mPa.s, and reproducibility is good.
[embodiment 2]
(manufacture of zinc catalyst)
Prepare to have cooler, dropping funel, nitrogen ingress pipe, as blender with 4 blade diameter 53mm
The paddle of (45 degree of inclinations) blade, internal diameter 80mm, 500mL volume round-bottomed flask.
N-hexane 87.1g, diethyl zinc 9.90g is added in flask after nitrogen displacement, inside with front end at 20 DEG C of temperature
Peripheral speed 0.97m/ seconds (speed of agitator 350rpm) is stirred, meanwhile, ethyl alcohol was added dropwise with 0.2g/ minutes on one side as the first stage
11.03g (0.240 mole), is reacted on one side.As second stage, by 1,4-butanediol 6.49g (0.072 mole) and second
The mixed liquor of alcohol 13.27g (0.288 mole) was added drop-wise to 0.2g/ minutes in the reaction solution for being cooled to 10 DEG C of interior temperature.Completion of dropwise addition
Afterwards, it will be warming up to 30 DEG C in flask to react 1 hour, then, be warming up to 50 DEG C and react 1 hour.Later, with 80 DEG C of oil bath temperature plus
Heat carries out the removing of unreacted component by distillation.It is let cool after distillation to room temperature, adds n-hexane 52.4g and with oil bath temperature
80 DEG C are heated, and the 2nd distillation is carried out.After 2 distillations, moves in the pressure vessel replaced by fully nitrogen, cover tightly
And with 130 DEG C of heat treatment for carrying out 15 minutes of oil bath temperature.After cooling, is diluted, obtained containing 1.8 matter with n-hexane 264g
Measure the zinc catalyst 297g of the zinc of %.The n-hexane of the supernatant of the zinc catalyst is measured by GC, as a result amount of alcohol relative to
Organic zinc compound is 0.0093 times of equivalent.
(manufacture of alkylene oxide polymer)
Prepare have dropping funel, nitrogen ingress pipe, the anchor type blade with blade diameter 47mm as blender
Paddle, internal diameter 94mm, 1L volume pressure-resistant reaction vessel.
N-hexane 340g is added in the pressure vessel after fully being replaced by nitrogen, makes zinc catalyst obtained above
(zinc converts 0.975g：0.0004 mole) it is uniformly dispersed, ethylene oxide 81g (1.84 moles) is added and covers tightly, at 40 DEG C
Thermostat in polymerize while stirring.After polymerization, white product is taken out in filtering, is dried under reduced pressure, obtains at 40 DEG C
Polyethylene oxide 78.6g.
Polymerization time is 45 minutes 6 hours, and yield is 97 mass %.The water of 0.5 mass % of obtained polyethylene oxide
The viscosity of solution is 820mPa.s.
[embodiment 3]
(manufacture of zinc catalyst)
Prepare to have cooler, dropping funel, nitrogen ingress pipe, as blender with 4 blade diameter 53mm
The paddle of (45 degree of inclinations) blade, internal diameter 80mm, 500mL volume round-bottomed flask.
N-hexane 87.1g, diethyl zinc 9.90g is added in flask after nitrogen displacement, inside with front end at 20 DEG C of temperature
Peripheral speed 0.97m/ seconds (speed of agitator 350rpm) is stirred, meanwhile, ethyl alcohol was added dropwise with 0.2g/ minutes on one side as the first stage
1.47g (0.030 mole), is reacted on one side.As second stage, by 1,4-butanediol 6.49g (0.072 mole) and ethyl alcohol
The mixed liquor of 13.27g (0.288 mole) was added drop-wise to 0.2g/ minutes in the reaction solution for being cooled to 10 DEG C of interior temperature.Completion of dropwise addition
Afterwards, it will be warming up to 30 DEG C in flask to react 1 hour, then, be warming up to 50 DEG C and react 1 hour.Later, with 80 DEG C of oil bath temperature plus
Heat carries out the removing of unreacted component by distillation.It is let cool after distillation to room temperature, adds n-hexane 52.4g and with oil bath temperature
80 DEG C are heated, and the 2nd distillation is carried out.1 operation is further carried out again, carries out total 3 distillations.After cooling, with just
Hexane 264g dilutions, obtain the zinc catalyst 297g of the zinc containing 1.8 mass %.The supernatant of the zinc catalyst is measured by GC
N-hexane, amount of alcohol relative to organic zinc compound be 0.0013 times of equivalent.
(manufacture of alkylene oxide polymer)
Prepare have dropping funel, nitrogen ingress pipe, the anchor type blade with blade diameter 47mm as blender
Paddle, internal diameter 94mm, 1L volume pressure-resistant reaction vessel.
N-hexane 340g is added in the pressure vessel after fully being replaced by nitrogen, makes zinc catalyst obtained above
(zinc converts 3.38g：0.0013 mole) it is uniformly dispersed, ethylene oxide 81g (1.84 moles) is added and covers tightly, at 40 DEG C
It polymerize while stirring in thermostat.After polymerization, white product is taken out in filtering, is dried under reduced pressure, is gathered at 40 DEG C
Ethylene oxide 80.9g.
Polymerization time is 15 minutes 4 hours, and yield is 100 mass %.The water of 0.5 mass % of obtained polyethylene oxide
The viscosity of solution is 810mPa.s.
[embodiment 4]
In the manufacture of the zinc catalyst of embodiment 3, whole vapo(u)rizing temperatures is changed to 70 DEG C from 80 DEG C, except this it
Outside, zinc catalyst is manufactured similarly to Example 3, obtains the zinc catalyst 297g of the zinc containing 1.8 mass %.It is measured by GC
The n-hexane of the supernatant of the zinc catalyst, as a result amount of alcohol is 0.0058 times of equivalent relative to organic zinc compound.
Similarly to Example 3, make (1.84 moles) polymerizations of ethylene oxide 81g using above-mentioned zinc catalyst, as a result obtain
Alkylene oxide polymer 77.9g.
Polymerization time is 30 minutes 4 hours, and yield is 96 mass %.The water of 0.5 mass % of obtained polyethylene oxide
The viscosity of solution is 595mPa.s.
[embodiment 5]
In the manufacture of the zinc catalyst of embodiment 3, whole vapo(u)rizing temperatures is changed to 100 DEG C from 80 DEG C, except this it
Outside, zinc catalyst is manufactured similarly to Example 3, obtains the zinc catalyst 297g of the zinc containing 1.8 mass %.It is measured by GC
The n-hexane of the supernatant of the zinc catalyst, amount of alcohol are 0.001 times of equivalent relative to organic zinc compound.
Similarly to Example 3, make (1.84 moles) polymerizations of ethylene oxide 81g using above-mentioned zinc catalyst, as a result obtain
Alkylene oxide polymer 80.2g.
Polymerization time is 5 hours, and yield is 99 mass %.The aqueous solution of 0.5 mass % of obtained polyethylene oxide
Viscosity is 720mPa.s.
[embodiment 6]
(manufacture of zinc catalyst)
Prepare to have cooler, dropping funel, nitrogen ingress pipe, as blender with 4 blade diameter 53mm
The paddle of (45 degree of inclinations) blade, internal diameter 80mm, 500mL volume round-bottomed flask.
N-hexane 87.1g, diethyl zinc 9.90g is added in flask after nitrogen displacement, inside with front end at 20 DEG C of temperature
Peripheral speed 0.97m/ seconds (speed of agitator 350rpm) is stirred, meanwhile, isopropyl was added dropwise with 0.2g/ minutes on one side as the first stage
Alcohol (2-PrOH) 14.42g (0.240 mole), is reacted on one side.As second stage, by 1,4-butanediol 6.49g (0.072
Mole) and the mixed liquor of isopropanol 17.31g (0.288 mole) reaction solution for being cooled to 10 DEG C of interior temperature was added drop-wise to 0.2g/ minutes
In.After completion of dropwise addition, it will be warming up to 30 DEG C in flask and react 1 hour, then, be warming up to 50 DEG C and react 1 hour.Later, with oil
80 DEG C of heating of bath temperature, the removing of unreacted component is carried out by distillation.It is let cool after distillation to room temperature, addition n-hexane 52.4g
And with oil bath temperature 80 DEG C heated, carry out the 2nd time distillation.1 operation is further carried out again, carries out total 3 distillations.
It after 3 distillations, moves in the pressure vessel replaced by fully nitrogen, covers tightly and with the progress 15 minutes of 130 DEG C of oil bath temperature
Heat treatment.After cooling, is diluted with n-hexane 264g, obtain the zinc catalyst 297g of the zinc containing 1.8 mass %.Pass through GC
The n-hexane of the supernatant of the zinc catalyst is measured, isopropanol amount is 0.0001 times of equivalent relative to organic zinc compound.
(manufacture of alkylene oxide polymer)
Prepare have dropping funel, nitrogen ingress pipe, the anchor type blade with blade diameter 47mm as blender
Paddle, internal diameter 94mm, 1L volume pressure-resistant reaction vessel.
N-hexane 340g is added in the pressure vessel after fully being replaced by nitrogen, makes zinc catalyst obtained above
(zinc converts 0.975g：0.0004 mole) it is uniformly dispersed, ethylene oxide 81g (1.84 moles) is added and covers tightly, at 40 DEG C
Thermostat in polymerize while stirring.After polymerization, white product is taken out in filtering, is dried under reduced pressure, obtains at 40 DEG C
Polyethylene oxide 75.7g.
Polymerization time is 45 minutes 6 hours, and yield is 93 mass %.The water of 0.5 mass % of obtained polyethylene oxide
The viscosity of solution is 575mPa.s.
[embodiment 7]
(manufacture of zinc catalyst)
Prepare to have cooler, dropping funel, nitrogen ingress pipe, as blender with 4 blade diameter 53mm
The paddle of (45 degree of inclinations) blade, internal diameter 80mm, 500mL volume round-bottomed flask.
N-hexane 87.1g, diethyl zinc 9.90g is added in flask after nitrogen displacement, inside with front end at 20 DEG C of temperature
Peripheral speed 0.97m/ seconds (speed of agitator 350rpm) is stirred, meanwhile, methanol was added dropwise with 0.2g/ minutes on one side as the first stage
1.02g (0.030 mole), is reacted on one side.As second stage, by 1,4-butanediol 6.49g (0.072 mole) and methanol
(MeOH) mixed liquor of 9.22g (0.288 mole) was added drop-wise to 0.2g/ minutes in the reaction solution for being cooled to 10 DEG C of interior temperature.It is added dropwise
After, it will be warming up to 30 DEG C in flask and react 1 hour, then, be warming up to 50 DEG C and react 1 hour.Later, with oil bath temperature 80
DEG C heating, pass through distillation carry out unreacted component removing.It is let cool after distillation to room temperature, adds n-hexane 52.4g and with oil bath
80 DEG C of temperature is heated, and the 2nd distillation is carried out.1 operation is further carried out again, carries out total 3 distillations.After cooling,
It is diluted with n-hexane 264g, obtains the zinc catalyst 297g of the zinc containing 1.8 mass %.The upper of the zinc catalyst is measured by GC
The n-hexane of clear liquid, as a result amount of alcohol is 0.0008 times of equivalent relative to organic zinc compound.
(manufacture of alkylene oxide polymer)
Prepare have dropping funel, nitrogen ingress pipe, the anchor type blade with blade diameter 47mm as blender
Paddle, internal diameter 94mm, 1L volume pressure-resistant reaction vessel.
N-hexane 340g is added in the pressure vessel after fully being replaced by nitrogen, makes zinc catalyst obtained above
(zinc converts 3.38g：0.0013 mole) it is uniformly dispersed, ethylene oxide 81g (1.84 moles) is added and covers tightly, at 40 DEG C
It polymerize while stirring in thermostat.After polymerization, white product is taken out in filtering, is dried under reduced pressure, is gathered at 40 DEG C
Ethylene oxide 79.1g.
Polymerization time is 30 minutes 5 hours, and yield is 98 mass %.The water of 0.5 mass % of obtained polyethylene oxide
The viscosity of solution is 425mPa.s.
[embodiment 8]
(manufacture of zinc catalyst)
Prepare to have cooler, dropping funel, nitrogen ingress pipe, as blender with 4 blade diameter 53mm
The paddle of (45 degree of inclinations) blade, internal diameter 80mm, 500mL volume round-bottomed flask.
N-hexane 87.1g, diethyl zinc 9.90g is added in flask after nitrogen displacement, inside with front end at 20 DEG C of temperature
Peripheral speed 0.97m/ seconds (speed of agitator 350rpm) is stirred, meanwhile, ethyl alcohol was added dropwise with 0.2g/ minutes on one side as the first stage
11.03g (0.240 mole), is reacted on one side.As second stage, by 1,4-butanediol 2.16g (0.30 mole) and ethyl alcohol
The mixed liquor of 26.54g (0.576 mole) was added drop-wise to 0.2g/ minutes in the reaction solution for being cooled to 10 DEG C of interior temperature.Completion of dropwise addition
Afterwards, it will be warming up to 30 DEG C in flask to react 1 hour, then, be warming up to 50 DEG C and react 1 hour.Later, with 80 DEG C of oil bath temperature plus
Heat carries out the removing of unreacted component by distillation.It is let cool after distillation to room temperature, adds n-hexane 52.4g and with oil bath temperature
80 DEG C are heated, and the 2nd distillation is carried out.1 operation is further carried out again, carries out total 3 distillations.After cooling, with just
Hexane 264g dilutions, obtain the zinc catalyst 297g of the zinc containing 1.8 mass %.The supernatant of the zinc catalyst is measured by GC
N-hexane, as a result amount of alcohol relative to organic zinc compound be 0.0048 times of equivalent.
(manufacture of alkylene oxide polymer)
Prepare have dropping funel, nitrogen ingress pipe, the anchor type blade with blade diameter 47mm as blender
Paddle, internal diameter 94mm, 1L volume pressure-resistant reaction vessel.
N-hexane 340g is added in the pressure vessel after fully being replaced by nitrogen, makes zinc catalyst obtained above
(zinc converts 3.38g：0.0013 mole) it is uniformly dispersed, ethylene oxide 81g (1.84 moles) is added and covers tightly, at 40 DEG C
It polymerize while stirring in thermostat.After polymerization, white product is taken out in filtering, is dried under reduced pressure, is gathered at 40 DEG C
Ethylene oxide 79.4g.
Polymerization time is 3 hours, and yield is 98 mass %.The aqueous solution of 0.5 mass % of obtained polyethylene oxide
Viscosity is 700mPa.s.
[embodiment 9]
(manufacture of zinc catalyst)
Prepare to have cooler, dropping funel, nitrogen ingress pipe, as blender with 4 blade diameter 53mm
The paddle of (45 degree of inclinations) blade, internal diameter 80mm, 500mL volume round-bottomed flask.
N-hexane 87.1g, diethyl zinc 9.90g is added in flask after nitrogen displacement, inside with front end at 20 DEG C of temperature
Peripheral speed 0.97m/ seconds (speed of agitator 350rpm) is stirred, meanwhile, Isosorbide-5-Nitrae-was added dropwise with 0.2g/ minutes on one side as the first stage
Butanediol 1.45g (0.016 mole), is reacted on one side.As second stage, by 5.04g (0.056 mole) and ethyl alcohol
The mixed liquor of 24.3g (0.528 mole) was added drop-wise to 0.2g/ minutes in the reaction solution for being cooled to 10 DEG C of interior temperature.After completion of dropwise addition,
It will be warming up to 30 DEG C in flask to react 1 hour, then, be warming up to 50 DEG C and react 1 hour.Later, with the heating of 80 DEG C of oil bath temperature,
The removing of unreacted component is carried out by distillation.It is let cool after distillation to room temperature, adds n-hexane 52.4g and with 80 DEG C of oil bath temperature
It is heated, carries out the 2nd distillation.1 operation is further carried out again, carries out total 3 distillations.3 times distillation after, move to by
Fully in the pressure vessel of nitrogen displacement, cover tightly and with 130 DEG C of heat treatment for carrying out 15 minutes of oil bath temperature.It is cooling
Afterwards, it is diluted with n-hexane 264g, obtains the zinc catalyst 297g of the zinc containing 1.8 mass %.The zinc catalyst is measured by GC
Supernatant n-hexane, as a result amount of alcohol relative to organic zinc compound be 0.0007 times of equivalent.
(manufacture of alkylene oxide polymer)
Prepare have dropping funel, nitrogen ingress pipe, the anchor type blade with blade diameter 47mm as blender
Paddle, internal diameter 94mm, 1L volume pressure-resistant reaction vessel.
N-hexane 340g is added in the pressure vessel after fully being replaced by nitrogen, makes zinc catalyst obtained above
(zinc converts 3.38g：0.0013 mole) it is uniformly dispersed, ethylene oxide 81.0g (1.84 moles) is added and covers tightly, at 40 DEG C
Thermostat in polymerize while stirring.After polymerization, white product is taken out in filtering, is dried under reduced pressure, obtains at 40 DEG C
Polyethylene oxide 80.8g.
Polymerization time is 30 minutes 4 hours, and yield is 100 mass %.The water of 0.5 mass % of obtained polyethylene oxide
The viscosity of solution is 815mPa.s.
[embodiment 10]
(manufacture of zinc catalyst)
Prepare to have cooler, dropping funel, nitrogen ingress pipe, as blender with 4 blade diameter 53mm
The paddle of (45 degree of inclinations) blade, internal diameter 80mm, 500mL volume round-bottomed flask.
N-hexane 87.1g, diethyl zinc 9.90g is added in flask after nitrogen displacement, inside with front end at 10 DEG C of temperature
Peripheral speed 0.97m/ seconds (speed of agitator 350rpm) is stirred, meanwhile, 1,4-butanediol 6.49g was added dropwise with 0.2g/ minutes
The mixed liquor of (0.072 mole) and ethyl alcohol 24.3g (0.528 mole).After completion of dropwise addition, 30 DEG C of reactions 1 will be warming up in flask
Hour, then, it is warming up to 50 DEG C and reacts 1 hour.Later, with 80 DEG C of heating of oil bath temperature, unreacted component is carried out by distillation
Removing.Let cool after distillation to room temperature, add n-hexane 52.4g and with oil bath temperature 80 DEG C heated, carry out the 2nd steaming
It evaporates.1 operation is further carried out again, carries out total 3 distillations.After cooling, is diluted, obtained containing 1.8 with n-hexane 264g
The zinc catalyst 297g of the zinc of quality %.The n-hexane of the supernatant of the zinc catalyst is measured by GC, as a result amount of alcohol is opposite
In organic zinc compound be 0.0038 times of equivalent.
(manufacture of alkylene oxide polymer)
Prepare have dropping funel, nitrogen ingress pipe, the anchor type blade with blade diameter 47mm as blender
Paddle, internal diameter 94mm, 1L volume pressure-resistant reaction vessel.
N-hexane 340g is added in the pressure vessel after fully being replaced by nitrogen, makes zinc catalyst obtained above
(zinc converts 3.38g：0.0013 mole) it is uniformly dispersed, ethylene oxide 81g (1.84 moles) is added and covers tightly, at 40 DEG C
It polymerize while stirring in thermostat.After polymerization, white product is taken out in filtering, is dried under reduced pressure, is gathered at 40 DEG C
Ethylene oxide 76.3g.
Polymerization time is 7 hours, and yield is 94 mass %.The aqueous solution of 0.5 mass % of obtained polyethylene oxide
Viscosity is 530mPa.s.
[comparative example 1-1]
(manufacture of zinc catalyst)
Prepare to have cooler, dropping funel, nitrogen ingress pipe, as blender with 4 blade diameter 53mm
The paddle of (45 degree of inclinations) blade, internal diameter 80mm, 500mL volume round-bottomed flask.
N-hexane 55.9g, higher boiling aliphatic hydrocarbon (trade name is added in flask after nitrogen displacement：Japan petroleum system 0
Number Solvent) 21.2g, diethyl zinc 9.90g, inside with front end peripheral speed 0.97m/ seconds (speed of agitator 350rpm) at 20 DEG C of temperature
It is stirred, meanwhile, ethyl alcohol 11.03g (0.240 mole) was added dropwise with 0.2g/ minutes on one side as the first stage, carries out on one side anti-
It answers.As second stage, by the mixed liquor of 1,4-butanediol 6.49g (0.072 mole) and ethyl alcohol 13.27g (0.288 mole) with
It is added drop-wise within 0.2g/ minutes in the reaction solution for being cooled to 10 DEG C of interior temperature.After completion of dropwise addition, it is small that 30 DEG C of reactions 1 will be warming up in flask
When, then, it is warming up to 50 DEG C and reacts 1 hour.Later, with oil bath temperature 130 DEG C carried out 15 minutes in the state of not lid lid
Heat treatment.After cooling, is diluted with n-hexane 264g, obtain the zinc catalyst 297g of the zinc containing 1.8 mass %.Pass through GC
The n-hexane of the supernatant of the zinc catalyst is measured, as a result amount of alcohol is 0.0116 times of equivalent relative to organic zinc compound.
(manufacture of alkylene oxide polymer)
Prepare have dropping funel, nitrogen ingress pipe, the anchor type blade with blade diameter 47mm as blender
Paddle, internal diameter 94mm, 1L volume pressure-resistant reaction vessel.
N-hexane 340g is added in the pressure vessel after fully being replaced by nitrogen, makes zinc catalyst obtained above
(zinc converts 0.975g：0.0004 mole) it is uniformly dispersed, ethylene oxide 81g (1.84 moles) is added and covers tightly, at 40 DEG C
Thermostat in polymerize while stirring.After polymerization, white product is taken out in filtering, is dried under reduced pressure, obtains at 40 DEG C
Polyethylene oxide 80.2g.
Polymerization time is 30 minutes 7 hours, and yield is 99 mass %.The water of 0.5 mass % of obtained polyethylene oxide
The viscosity of solution is 825mPa.s.
[comparative example 1-2]
Zinc catalyst is manufactured in the same manner as comparative example 1-1, obtains the zinc catalyst 297g of the zinc containing 1.8 mass %.It is logical
The n-hexane that GC measures the supernatant of the zinc catalyst is crossed, as a result amount of alcohol is worked as relative to organic zinc compound for 0.0334 times
Amount.
In the same manner as comparative example 1-1, make (1.84 moles) polymerizations of ethylene oxide 81g using above-mentioned zinc catalyst, as a result
To polyethylene oxide 79.8g.
Polymerization time is 15 minutes 11 hours, and yield is 99 mass %.The water of 0.5 mass % of obtained polyethylene oxide
The viscosity of solution is 625mPa.s.
[comparative example 1-3]
Zinc catalyst is manufactured in the same manner as comparative example 1-1, obtains the zinc catalyst 297g of the zinc containing 1.8 mass %.It is logical
The n-hexane that GC measures the supernatant of the zinc catalyst is crossed, amount of alcohol is 0.00221 times of equivalent relative to organic zinc compound.
In the same manner as comparative example 1-1, make (1.84 moles) polymerizations of ethylene oxide 81g using above-mentioned zinc catalyst, as a result
To polyethylene oxide 78.3g.
Polymerization time is 45 minutes 9 hours, and yield is 97 mass %.The water of 0.5 mass % of obtained polyethylene oxide
The viscosity of solution is 785mPa.s.
[table 1]
* 1：In table 1, Isosorbide-5-Nitrae-BDO is not monohydric alcohol, but is documented in one column of monohydric alcohol for convenience of description.
[table 2]
As indicated in the result shown in table 1 and table 2, according to embodiment 1-1,1-2,1-3 and comparative example 1-1,1-2,1-3
Compare it is found that in the manufacture of zinc catalyst, by carrying out distillation processing, makes the amount of the monohydric alcohol in zinc catalyst relative to having
Machine zinc compound is 0.01 times of equivalent hereinafter, reproducibility obtains alkylene oxide polymer well as a result,.That is, can according to the result
Know, in order to obtain the high alkylene oxide polymer of the degree of polymerization with good reproducibility, needs through the heat treatment advance in zinc catalyst
Row distillation, monohydric alcohol amount is removed to specified value.In addition, in embodiment 2~10, similarly it is identified through and is set as 0.01
Times equivalent is hereinafter, the high alkylene oxide polymer of the degree of polymerization industrially can be manufactured efficiently.
Claims (6)
1. a kind of manufacturing method of alkylene oxide polymer is to make alkylene oxide in the presence of zinc catalyst in unreactive hydrocarbons solvent
The method for carrying out polymerisation and manufacturing alkylene oxide polymer, has：
Make organic zinc compound with relative to the organic zinc compound be 12 times of equivalents monohydric alcohol below and 0.2~1.1 times
The aliphatic polyol of equivalent reacts, the process for preparing reaction solution；
By the reaction solution under normal pressure, 100 DEG C of temperature or less distill, make the amount of the monohydric alcohol relative to described organic
Zinc compound is 0.01 times of equivalent hereinafter, later, heating 5~15 minutes at 100~130 DEG C, preparing zinc catalyst
Process；And
Using the monohydric alcohol amount relative to the organic zinc compound be 0.01 times of equivalent zinc catalyst below, make
The process of the alkylene oxide polymerization reaction.
2. the manufacturing method of alkylene oxide polymer according to claim 1, wherein
The organic zinc compound is dialkyl group zinc.
3. the manufacturing method of alkylene oxide polymer according to claim 1 or 2, wherein
The monohydric alcohol is the aliphatic alcohol of carbon atom number 1~3.
4. the manufacturing method of alkylene oxide polymer according to claim 1 or 2, wherein
The aliphatic polyol is the aliphatic polyol with 2 or more hydroxyls during carbon atom number is 2 or more and molecule.
5. a kind of manufacturing method of the zinc catalyst of polymerisation for alkylene oxide, has：
Make organic zinc compound with relative to the organic zinc compound be 12 times of equivalents monohydric alcohol below and 0.2~1.1 times
The reaction process of the aliphatic polyol reaction of equivalent；
By the reaction solution obtained by the reaction process under normal pressure, 100 DEG C of temperature or less distill, make the monohydric alcohol
Amount relative to the organic zinc compound be 0.01 times of equivalent hereinafter, later, heat 5~15 points at 100~130 DEG C
The process of clock.
6. a kind of zinc catalyst of polymerisation for alkylene oxide, is obtained with following process,
Make organic zinc compound with relative to the organic zinc compound be 12 times of equivalents monohydric alcohol below and 0.2~1.1 times
After the aliphatic polyol reaction of equivalent, obtained reaction solution is distilled under normal pressure, below 100 DEG C of temperature, make described in
The amount of monohydric alcohol relative to the organic zinc compound be 0.01 times of equivalent hereinafter, later, heating 5 at 100~130 DEG C
~15 minutes.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2014-072760 | 2014-03-31 | ||
| JP2014072760 | 2014-03-31 | ||
| PCT/JP2015/053777 WO2015151598A1 (en) | 2014-03-31 | 2015-02-12 | Alkylene oxide polymer production method |
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| CN106103546B true CN106103546B (en) | 2018-11-06 |
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| US (2) | US20170096527A1 (en) |
| EP (1) | EP3127935B1 (en) |
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| WO2023145864A1 (en) * | 2022-01-31 | 2023-08-03 | 住友精化株式会社 | Polyalkylene oxide particle, pharmaceutical composition, composition for preparation, and preparation |
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| US5326852A (en) * | 1991-07-11 | 1994-07-05 | Sumitomo Seika Chemicals Co., Ltd. | Method for production of alkylene oxide polymers |
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| JPS457751Y1 (en) | 1966-08-20 | 1970-04-14 | ||
| JPS5327319B1 (en) | 1971-01-11 | 1978-08-08 | ||
| JPS5831055B2 (en) | 1976-08-26 | 1983-07-04 | 松下電器産業株式会社 | Television receiver program control device |
| AU7077287A (en) | 1986-03-31 | 1987-10-08 | Union Carbide Corporation | Alkylene oxide polymerisation catalyst |
| JP2002265592A (en) * | 2001-03-07 | 2002-09-18 | Sumitomo Seika Chem Co Ltd | Process for producing alkylene oxide polymer |
| CN103562265B (en) | 2011-06-03 | 2016-03-16 | 住友精化株式会社 | Polyalkylene oxide particle and manufacture method thereof |
| WO2012165199A1 (en) * | 2011-06-03 | 2012-12-06 | 住友精化株式会社 | Polyalkylene oxide particles and production method for same |
| KR20160089381A (en) * | 2013-11-22 | 2016-07-27 | 다우 글로벌 테크놀로지스 엘엘씨 | Zinc catalyst/additive system for the polymerization of epoxide monomers |
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| US5326852A (en) * | 1991-07-11 | 1994-07-05 | Sumitomo Seika Chemicals Co., Ltd. | Method for production of alkylene oxide polymers |
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| KR102254691B1 (en) | 2021-05-21 |
| KR20160140707A (en) | 2016-12-07 |
| CN106103546A (en) | 2016-11-09 |
| EP3127935A4 (en) | 2017-11-08 |
| EP3127935B1 (en) | 2020-05-27 |
| US20170096527A1 (en) | 2017-04-06 |
| WO2015151598A1 (en) | 2015-10-08 |
| JP6630662B2 (en) | 2020-01-15 |
| TWI655225B (en) | 2019-04-01 |
| US20180319933A1 (en) | 2018-11-08 |
| US10329382B2 (en) | 2019-06-25 |
| JPWO2015151598A1 (en) | 2017-04-13 |
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